Post on 01-Apr-2015
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Dr. Max MustermannReferat Kommunikation & Marketing Verwaltung
Gábor BalázsInstitute of Inorganic ChemistryUniversity of Regensburg
COMPLEXES WITH TERMINALLY
COORDINATED EQ (E = P, As; Q = S, Se, Te)
LIGANDS
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Contents
• Introduction
• Complexes with W≡E (E = group 15 element) triple bonds
• Synthesis of complexes with linearly coordinated EQ ligands (Q = group 16 element)
• Reactivity of linearly coordinated EQ Complexes
• Summary
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N O N O
O
N
LnM
LnM
ON
MLnLnM
ON
MLnLnM
LnMN
O
P O P O
EQE = P, As, Sb, BiQ = O, S, Se, Te
Coordination modes of NO
Gábor BalázsUniversity of Regensburg
ICOMC 2010
LnM + EQ
Q
E
LnME = P, As, Sb, BiQ = O, S, Se, Te
Possible synthetic roots for complexes with η1-EQ ligands
Gábor BalázsUniversity of Regensburg
ICOMC 2010
O. J. Scherer, J. Braun, P. Walther, G. Heckmann, G. Wolmershaeuser, Angew. Chem., 103, 1991, 861.O. J. Scherer, C. Vondung, G. Wolmershauser, Angew. Chem. Int. Ed. Engl., 36, 1997, 1303.O. J. Scherer, S. Weigel, G. Wolmershauser, Heteroat. Chem., 10, 1999, 622.J. F. Corrigan, S. Doherty, N. J. Taylor and A. J. Carty, J. Am. Chem. Soc., 116, 1994, 9799.J. E. Davies, M. J. Mays, E. J. Pook, P. R. Raithby, P. K. Tompkin, Chem. Commun., 1997, 1997.C. E. Laplaza, W. M. Davis, C. C. Cummins Angew. Chem. Int. Ed. Engl. 1995, 34, 2042.M. J. A. Johnson, A. L. Odom, C. C. Cummins Chem. Commun., 1997, 1523.
CartyLnMMLn
LnMMLn
P
MLn
O
MLn = Ru(CO)3
CpRNiP
PNiCpR
W Q
Q
(CO)4
Q = O, S
MLn
LnM MLn
P
S
MLn = CpMo(CO)2MLn = CpW(CO)2
Mays
MLn
LnM MLn
P
Q
Q = O, S, Se
P
Q
MLn
LnM MLn
P
Q
P
Q = Se, Te
MLn = Cp''Co; Cp'' = C5H3tBu-1,3 Scherer
Cummins
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Complexes with Terminal Phosphido, Arsido and Antimonido Ligands
Schrock Cummins Scheer
N WN
N
P
N
Me3SiSiMe3
SiMe3
Ph''RNMo
NRPh''
NRPh''
P RO
WRO
RO
P W(CO)5
R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl. 1995, 34, 2044.C. E. Laplaza, W. M. Davis, C. C. Cummins Angew. Chem. Int. Ed. Engl. 1995, 34, 2042.M. Scheer, K. Schuster, T. A. Budzichowski, M. H. Chisholm, W. E. Streib Chem. Commun. 1995, 1671.
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
P
N
Me3SiSiMe3
SiMe3N WN
N
Cl
N
Me3SiSiMe3
SiMe3 + 2 LiP(H)Ph
R. R. Schrock, N. C. Zanetti, W. N. Davis Angew. Chem. Int. Ed. Engl. 1995, 34, 2044.M. Scheer, J. Müller, M. Häser Angew. Chem. 1996, 108, 2637.
Gábor BalázsUniversity of Regensburg
ICOMC 2010
M. Scheer, J. Müller, G. Baum, M. Häser Chem. Commun. 1998, 2505.M. Scheer, J. Müller, M. Schiffer, G. Baum, R. Winter Chem. Eur. J. 2000, 6, 1252.
N
W
N N
EN
R
RR
N WN
N
Cl
N
RR
R + 2 LiE(SiMe3)2
E = Sb, Bi
N
W
NN
N
R
R R
R = CH2C(CH3)3
W-Sb 2.574(1) Å
Gábor BalázsUniversity of Regensburg
ICOMC 2010
13C NMRδ = 319.4 ppm (W≡C)
W(1)-C(19) 1.813(1)Å
N WN
N
C
N
Me3SiSiMe3
SiMe3N WN
N
Cl
N
Me3SiSiMe3
SiMe3
Sb
CH2
H
SiMe3
Li
SiMe3
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
Sb
N
Me3SiSiMe3
SiMe3N WN
N
Cl
N
Me3SiSiMe3
SiMe3
Sb
CH
H
SiMe3Me3Si
Li
G. Balázs, M. Sierka, M. Scheer Angew. Chem. Int. Ed. 2005, 44, 4920.
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Bond lengths (Å) and Angles (°):
Exp. Calc. W – Sb 2.525(2) 2.514 W – Neq 1.994(8) 2.015
W – Nax 2.33(1) 2.516
Neq – W – Sb 101.8(2) 104.1
Nax – W – Sb 180.0 –
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
E
N
RR
RN WN
N
Cl
N
RR
R
iPr
iPr
iPr
iPr
iPr
iPr
R =
+ 2 LiEH2
·
E = P, As
N WN
N
E
N
RR
R
EE
Gábor BalázsUniversity of Regensburg
ICOMC 2010
W–P 2.142(1) Å
31P NMR: δ = -188 ppm31P NMR: δ = 1239 ppm
W–As 2.258(1) Å
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N
WN
NN
R
RP
iPr
iPr
iPr
iPr
iPr
iPr
II
N WN
N
P
N
RR
R+ I2
·
W–P 2.544(3) ÅW–I 2.7434(9) ÅP–I 2.729(3) and 2.795(3) Å
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
E
N
Me3SiSiMe3
SiMe3N WN
N
E
N
Me3SiSiMe3
SiMe3
S
S
E = P, As
G. Balázs, J. C. Green, M. Scheer Chem. Eur. J. 2006, 12, 8603.G. Balázs, J. C. Green, D. M. P. Mingos Eur. J. Inorg. Chem. 2007, 2443.
31P NMR: δ = 342.3 ppm; 1JPW = 771.5 Hz
31P NMR: δ = 1080.3 ppm; 1JPW = 138 Hz
Terminally Coordinated EQ Complexes
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
P
N
Me3SiSiMe3
SiMe3N WN
N
P
N
Me3SiSiMe3
SiMe3
Se
+ Se ·
Toluene, rt.
quantitative yield
Gábor BalázsUniversity of Regensburg
ICOMC 2010
31P{1H} NMR
N WN
N
P
N
Me3SiSiMe3
SiMe3
Te
N WN
N
P
N
Me3SiSiMe3
SiMe3
Se
1JPSe = 790 Hz1JPW = 727 Hz
1JPTe = 1759 Hz1JPW = 649 Hz
Gábor BalázsUniversity of Regensburg
ICOMC 2010
31P{1H} NMR
Gábor BalázsUniversity of Regensburg
ICOMC 2010
DFT Optimized (RI-DFT, BP86, SV(P)) Transition State Structure
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
P
N
Me3SiSiMe3
SiMe3N W
N
N
P
N
Me3SiSiMe3
SiMe3
Se
+
Gábor BalázsUniversity of Regensburg
ICOMC 2010
P As
S Se Te S
W–E 2.158(1) 2.152(1) 2.159(1) 2.256(1)
E–Q 1.940(2) 2.081(1) 2.294(1) 2.048(2)
W–E–Q 177.1(4) 177.3(1) 176.6(1) 177.6(1)
Nax–W–E 178.0(4) 178.3(1) 177.8(1) 178.7(2)
Selected bond lengths (Å) and angles (°)
(N3N)W ≡ E
W–P 2.162(4)W–As 2.290(1)
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Single Marks
N WN
N
E
N
Me3SiSiMe3
SiMe3
Q
N WN
N
E
N
Me3SiSiMe3
SiMe3
Gábor BalázsUniversity of Regensburg
ICOMC 2010
P As Sb Bi−482 −429 −333 −293
σ W-E-Q Hybrid.E = P sp0.5 E = Bi sp0.7
σ W-E Hybrid.E = P sp3.3 E = Bi sp6.6
N WN
N
E
N
Me3SiSiMe3
SiMe3
Q
N WN
N
E
N
Me3SiSiMe3
SiMe3
Q P As Sb Bi
O −415 −341 −259 −204
S −401 −339 −262 −207
Se −400 −339 −259 −205
Te −401 −340 −261 −208
W–E Bond Dissociation Energies (kJ·mol−1)
W–E Bond Dissociation Energies (kJ·mol−1)
Gábor BalázsUniversity of Regensburg
ICOMC 2010
O S Se Te
P -558 -349 -287 -212
As -439 -302 -255 -197
Sb -383 -281 -244 -190
Bi -326 -248 -219 -173
E–Q Bond Dissociation Energies (kJ·mol−1)
N WN
N
E
N
Me3SiSiMe3
SiMe3
Q
N WN
N
E
N
Me3SiSiMe3
SiMe3
Q P As Sb Bi
O −415 −341 −259 −204
S −401 −339 −262 −207
Se −400 −339 −259 −205
Te −401 −340 −261 −208
W–E Bond Dissociation Energies (kJ·mol−1)
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
As
N
Me3SiSiMe3
SiMe3
S
Molecular Orbital Interaction Diagram
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
As
N
Me3SiSiMe3
SiMe3
S
Molecular Orbital Interaction Diagram
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Comparative MO Diagram in Complexes N3NW(PQ)
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Q E W–E E–Q
O P 2.12 2.07
As 2.09 1.97
Sb 2.12 2.13
Bi 2.14 2.18
S P 2.22 2.03
As 2.24 1.83
Sb 2.20 2.12
Bi 2.23 2.10
Se P 2.24 1.98
As 2.26 1.82
Sb 2.23 2.09
Bi 2.26 2.08
Te P 2.32 1.92
As 2.33 1.73
Sb 2.28 2.05
Bi 2.30 2.06
P = ,♦ As = , ■ Sb = , ▲ Bi = ●
Hirshfeld Charge Distribution: Positive on W and Negative on Q
Fractional Bond Orders
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
P
N
Me3SiSiMe3
SiMe3
Te
+
N
N
iPr
iPr
iPr
iPr
N
N
iPr
iPr
iPr
iPr
Te + N WN
N
P
N
Me3SiSiMe3
SiMe3
Reactivity of N3NW(PTe)
Gábor BalázsUniversity of Regensburg
ICOMC 2010
N WN
N
P
N
Me3SiSiMe3
SiMe3
Te
+ W
PCy3
PCy3OC
COOC
N WN
N
P
N
Me3SiSiMe3
SiMe3
W
NWN
N
P
N
SiMe3Me3Si
Me3Si
OC
OC CO
CO
Reactivity of N3NW(PTe)
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Conclusions
• Synthesis of complexes containing linearly coordinated EQ ligands of the heavier group 15 and 16 Elements is possible
•The [(N3N)W(PTe) complex can readily be used as a tellurium transfer reagent
• The π system can be best described as two orthogonal three centered two electron system
Gábor BalázsUniversity of Regensburg
ICOMC 2010
Acknowledgment
• Prof. Dr. M. Scheer
• Prof. Dr. J. C. Green
• Prof. Dr. D. M. P. Mingos
• Alexander von Humboldt Foundation
• Deutsche Forschungsgemeinschaft
• University of Regensburg
Thank you for your attention